Manufacture of organic substances of very high molecular weight



Feb. 16,

D. R. JOHNSTON MANUFACTURE OF ORGANIC SUBSTANCES OF VERY HIGH MOLECULAR WEIGHT Filed Feb. 25. 1955 0 v'oHA/s ro/v m mvrok .MANUFACWEOFORGANIC SUBSTANCES F VERY HIGH MOLECULAR WEIGHT "David Robert Johnston, Spondon, .nearDerby, England,

ass gnor to British Celanese;Limited acorporation of GreatBritain I t Application February 25, 1 95s, Serial Noi j49tL617r Claims" priority, pplication Great Britain Marchz; 1-954 8fClaims. iicr 2604230) the momentum of the unsupp'ortedstrams.) v

In the preferred method of carrying; out the :inyem which is capable of absorbing at least the. greater tion the unsupported streams of -solution and l-precipitant are substantially parallel and,;in contact, and! ,the stream or streams of solution -are -preterablysurrounded byga ,stream-or'streams of precipitant.

While the unsupported streams of solution aind precipitant may remain :quite disinct untiltthey reach Qthfe. surface of the body" of- .precipitant, 1a. certain amount of mi xing may take placein advance of this surfac'e.-- v-When the streams are substantially parallel and in;;con,tact h each lotherga degreeofi-mixing willas a rule take-Place without the use of any; special; means "to 'promote;iit,:e s'- peciallywhen, as is .preferred,-a stream of solution travels 7 more slowly than a surrounding streamer-streams 10f precipitant, The degree to which such; mixing "takes place may however be increased by means ;adapted to promote turbulent -;fiow in one; or more of the streams ;,or

In nearly all the processesiused .forlmaking. cellulose esters of organic acids, the cellulose ester is-obtainedin solution. ,Usually. the solvent {is aloyver aliphatic iacid, especially acetic;acid,..whieh may .contain ,a, proportion of water, but it may for example: be methylene chloride or ethylene chloride. The..- cellulose ester-"is vprecipitated from the solutionfiby means vof a=: suitable .nontsolvent; .thus it may be precipitated l'fromeolution-in .aceticacid .b'ytmeans of .waterloransaqueous acetic acid .Qf: concentration belowabout 40%. f 1 v "The conditions under which the cellulose ester'gis pre- .cipitated are ;irnpor,tant,.,for ;on themadependsthe form of precipitateobtained. It is :forunost purposes very ide- 'sirable, to avoid the formation ofahorny hard'precip- 'itate, sincein this forrncellulose esters are difficult or virtually impossible to wash properly, and: even-after prolonged washing may. contain an unacceptably high proportion ,ofaacid and other, impurities. On the other -hand, cellulose esters precipitatedinthe form 0f 8. fibrous flake (are. easy; to- -was h,';and this-is a form to be aimed at. I I

.The present,inventiomprovides asimple-method of precipitating .from their solutions cellulose'acetate and ,othercelluloseesters ofrorganicracids, by means of which rthe precipitate ;can gbe-aobtained in an easilyswashed by causing the streams to converge slightly.

' lt is usually convenient that the- ;pr eci pitant, in the :unsupported-stream or streams and that in the;;body .of'pre- 'cipitantshould it either be TldCHtlCaP-QI', it'they are mixtures, should at least contain the samechemicalvyinstreamstof aqueous acetic acid;ithejbody-;of-;mprecipitant precipitating other organic substances of veryhighmolecinlarweight t United States application 1Ser.-: No.":4,17 ,170 describes aa-rnethod .of precipitating cellulose esters and other. subistances of very high'-:molecularz.= weight fromitheir solua ,tions; -;in which unsupported streams of the solution 'and iDf'ra precipitant are rapidly :andz'intimately intermixed. This mixing, may i be effected l by) collision between the streams, especially substantially head-oncollision, but

iris preferably -,-elfected f by causing (unsupported: streams 'ofithe solution and :precipitant to impinge simultane- -.;ously=:on the same areapor on immediately adjacent areas '::of azsolidsurface. I

. According to thepresent invention, organicsubstance's -.ofivery high molecular weight especially cellulose esters Lof organic :acids, are =-pre cipitated"from" their "solutions by lcausing unsupported streams ofthe solution and of a precipitant,to irnpinge simultaneously on the same or is preferably also aqueous acetic acid, though git-may be of adiflerent concentration. It isof course;necessary-in 311563868 that-the liquid resultingfromithe mixturewof ve t. pr eir t s e m andithetbo ylot p eip n should itself the ga precipitant. Advantageously the ;amount-of precipitant in the unsupported t,s tream.:.or

streams is atsleast ;suc h-as would be: suflicient to ipreoip itate substantially the whole :of -;;the 5 organic substance from. the solutionr if intimately IIliXBdWllh: the solution in the-absence of thebody of :precipitant.

For the sake of brevity, atheinvention will be further described with particular reference 'tothe precipitation of; cellulose acetate, from its 3 solutions, especially; from solutions such; as. are obtained ;in; the manufacture; of the cellulose acetate.

t The cellulose. acetate solution may be extrudedflto gform jthesunsupportedstream or streamseitherat room temperature or tat-a higher temperature, which maybe below otabove theboilingpointof the solvent. -,'F,or example, solutions, ofcelluloseqacetate gin-aacetic acid which have been ripened at an elevated temperaturqezg.

,a temperaturebetween about 509;andv80 =C mayaoften .convenientlygbe extruded at. about the ripening temperature... The precipitant ;may;,be-,at;aboutithe1same temperature asthe cellulose acetate solution,'or :it may be at ,a higher or,lower;temperature.- the precipitantor both may be heated to ,a temperature The solution ;,or

such that part :or all .of the solvent isqvapourised as or after: the: streams of solution and precipitant impingeton the body of precipitant,- especially., whe'n: ,a low; boiling solvent such as methylene chloride -;is used.

,The formofthe precipitate may be varied to some extent by varying the temperature v.of the s olution; -:thus if a precipitate is, required which, while retaining the ,fibrous-fiaketorm characteristic of the. ;invention,; has at :the same timer-a high -bulk, density, the solution should beat a fairly=low temperature, e.g. betweenabout-20 .and 40 or 50" C. :when; precipitating; cellulose a cetate from solution inacetic-,iacidlbynreans of water or an aqueous acetic acid; conversely if a precipitate of. low bulk density is required, the solution should :beat: ahigher temperature, e g. between aboutI60 and CL-or-even ,higher.

I Uniwd, s? Pat ioifice 3 which it is extruded issuch that it is capable of being formed into a fairly rapidly flowing stream without using an indesirably high pressure, and if in any instance the viscosity is too high for this, the solution may bethinned with further quantities of solvent for the cellulose acetate. The invention includes not only the new precipitation -method, but also devices for carrying it out comprising a vessel adapted to contain a body of liquid, means for withdrawing liquid containing solids in suspension from the said vessel while, maintaining the surface of a body of liquid in the vessel at a constant level, and a nozzle adapted to form streams of solution and precipitant in the said vessel, the arrangement being such that the any tendency for solids to collect either at the surface of the liquid in the vessel or at the bottom of the vessel, according to the respective densities of the solid and liquid. In one form of device which has been found to give 'very good results, the cellulose acetate or other solution and the precipitant are continuously extruded at a fairly high rate of flow through a multiple nozzle comprising a central orifice, preferably an annulus, surrounded by two or more annular orifices which are preferably concentric with the central orifice, alternate orifices serving to form streams of solution and precipitant respectively. Advantageously there may be used a triple nozzle comprising a central orifice, preferably an annulus, surrounded by two annular orifices concentric with it, the precipitant being extruded through the innermost (i.e. the central) and the outermost orifices, and the cellulose acetate solution through the middle orifice. By this means there is obtained a stream of annular crosssection of the cellulose acetate solution, which is bounded on both sides by a stream of precipitant. Other arrangements can however be used. For exampde a nozzle having only a central circular or annular orifice and an outer annular orifice may be used, the cellulose acetate solution then being extruded preferably through the central orifice, and the precipitant through the surrounding annular orifice. Again, the solution and the precipitant may be extruded through adjacent parallel slots; if the nozzle contains three such slots, the solution may be extruded through the medial slot and the precipitant through the two lateral slots. Adjacent orifices of other shapes, e.g. circular orifices, can be used, though in general with less advantage. For the purpose of the present specification all such extrusion devices are included within the term nozzles.

Whatever form of nozzle is used, the lips of the orifices may be so formed as to promote a smooth flow of the several streams with little or no intermixing before they reach the surface of the body of precipitant, or they may be shaped so as to cause the streams to converge slightly or to create a substantial degree of turbulence in one or more of the streams, and so to promote a substantial de gree of mixing before the streams reach the surface of the precipitant body. The streams may inpinge on the liquid surface vertically or at an angle to the vertical.

The vessel in which the precipitation is carried out may suitably have the form of a vertical cylinder, and may be provided with an overflow outlet at the level desired for the surface of the body of precipitant during operation. The nozzle may conveniently open into or extend through the top of the vessel. The vessel may also be provided with an inlet for initially introducing the body of precipitant, and this inlet may if desired also serve for the continuous introduction of further precipitant during the precipitation. If in any particular case it is desired to work under conditions such that part or all of the solvent is vaporised, the vessel may be provided with a separate outlet through which the solvent vapou 9 bi.- Withdrawn- The precipitating vessel may discharge into a collecting vessel in which the precipitate is separated from the liquid, e.g. by decantation, or it may discharge onto a device, such for example as a shaking screen, by means of which the precipitate may be separated from the liquid continuously. After being separated from'the liquid the precipitate can be washed and if desired given further treatment; for instance a cellulose ester may be given a stabilisation treatment.

Apparatus in accordance with the invention is illustrated in the accompanying drawing, in which:

Figure 1 is a sectional elevation of a precipitating device as a whole,

Figure 2 is a sectional elevation, on a larger scale and in greater detail, of the nozzle shown in Figure 1,

Figure 3 is a plan view of another form of nozzle,

Figure 4 is a sectional view taken on the line 4--4 in Figure 3, and

Figure 5 is a sectionaljelevation of a third form of '10'into which leads an inlet pipe 11 for liquid, and from which an overflow discharge duct 12 leads to a separating vessel or a shaking screen (not shown). A drain 12A leads from the bottom of the vessel. The vessel 10 is provided with a jacket 13 through which a heating or cooling fluid may be passed. A propeller-type stirrer 14 near the bottom of the vessel 10 is carried on a vertical shaft 15 driven in any suitable way. A nozzle 16 extends vertically through, the top of the vessel 10 about half way between the axis and the wall of the vessel, and is provided with feed pipes 17 and 18 for precipitant and a feed pipe 19 for the solution to be precipitated. The feed pipes 17 and 18 are themselves fed from a common feed line 20.

The nozzle 16, as shown in greater detail in Figure 2, comprises three co-axial tubes 21, 22 and 23, the innermost tube 21 being the longest and the outermost tube '23 the shortest. An annular end-piece 24, fitting closely round the innermost tube 21, closes one end of the middle tube 22, and a similar end-piece 25, fitting closely round the middle tube 22, closes the corresponding end of the outermost tube 23. The corresponding end of the innermost tube 21 carries a flange 26 by means of which the nozzle is attached to the precipitant feed pipe 17.

The tube 21 is provided with a fixed collar 27, secured by bolts 28 to a flange 29 on the end of the middle tube 22,'the collar 27 being just clear of the end piece :24. An inlet pipe 30 enters the tube 22 ,near its closed end, and carries a flange 31 whereby it is attached to the solution feed pipe 19.

The tube 22 is provided with a fixed collar 32, secured by bolts 33 to a flange 34 on the end of the tube 23, the collar 32 being just clear of the end piece 25. An inlet pipe 35 enters the tube 23 near its closed end, and carries a flange 36 whereby it is attached to the precipitant feed pipe 18. The tube 23 is attached to the top 37 of the vessel 10 by fins 38, one of which is also attached to the inlet pipe 35.

At their output ends the tubes 21, 22 and 23 are welded to externally threaded connecting sections 39, 40 and 41 respectively, onto which are screwed internally threaded annular members 42, 43 and 44 respectively, so shaped as to form a narrow annular orifice 45 bounded by the lips of the outermost member 44 and the middle member 43, and another narrow annular orifice 46, bounded by the lips of the middle member 43 and the innermost member 42. Fins 47 are provided in the passages 48', 49 leading to these orifices- An externally threaded tubular member 50 is screwed into the innermost annular member 42 and in effect forms a short extension of the innermost tube 21. At its end the tubular member 50 carries a circular disc 51 having a hexagon boss 52 the diameter of the disc 51 being night-1y fessuian" theifiterna'fdiameter O fffli innermost annular member 42 at its lip', so thatitforms' therewith: I Ports 54 adjacent to thedisc 51 lead from the interior of the a third and innermost annularorifice 53;

tubular member 50 to the annular passage 55 between the forward ends of the tubular member 50 and the innermost annular member '42.

In operation, precipitant is fed int'o the vessel through the inlet 11 upfto the level of the overflow dis-' charge duct 12, and the stirrer 13 is started; The cellulose acetate or other solution mbe precipitated is the innermost orifice-53, and alsothrough the feed pipe 18, the inlet 35,-the space-between theoutermost tube 23 and the middle tube 22, andthe passage'48 to the outermost orifice 4 5. Preferablythestreams-of precipitant leave theorifices 45 and 53' ata linear' speed higherthan that at'which the solution leaves theorifice 46, though-this is not essential. The streamsof precipitant andsolution impinge on the surface of the body of precipitant in the vessel 10, and are rapidly mixed with each other and with the precipitant already in the vessel, precipitating the cellulose acetate in an easily washed fibrous form; the slurry of precipitate soproduced, which may if desired be diluted with further precipitant introduced through the inlet 11, leaves the vessel by the discharge duct 12 and passes to a settling vessel or a shaking screen. The vessel can when desired be emptied of liquid, e.g. for cleaning, by means of the drain 12A.

Another type of nozzle, that may be employed in place of that illustrated in Figure 2, is shown diagrammatically in Figures 3 and 4. In this nozzle the orifices have the form of narrow parallel slots. The nozzle comprises an outercylindrical member 61 provided with a liquid inlet 62 and, opposite to it, a fairly wide passageway 63 of rectangular cross-section extending along the whole length of the member 61 and terminating in a somewhat narrower opening 64. Inside the cylindrical member 61 is a coaxial second cylindrical member 65 of smaller diameter, fed by a pipe 66 passing through the outer member 61. The cylindrical member 65 opens into a passageway 67 of rectangular cross-section extend ing along the whole length of the member 65 and situated symmetrically within the passageway 63; the passageway 67 narrows to a slot-like orifice 68, the lips of which form with the lips of the opening 64 two further slot-like orifices 69 and 70 symmetrically situated on either side of the orifice 68. The cylindrical members'61 and 65 are closed by common end walls 71.

In working with the nozzle shown in Figures 3' and 4 a cellulose acetate solution to be precipitated is pumped .through the feed pipe 66 to the inner cylindrical member A third form of nozzle is illustrated in Figure 5, and

comprises a cylindricaltubular member 81 having at one end an inlet 82 for liquid, and tapering at the other end to a circular orifice 83. The tubular member 81 is surrounded by a second and coaxial tubular member 84 provided with a liquid inlet 85 and forming with the tubular member 81 an annular passageway 86. This annular passageway is closed at the end nearer the inlet 82 by means of an end wall 87 fitting closely round the tubular member 81, and at the other end it tapers to form an annular orifice 88 concentric with the circular orifice 83.

Imwark'ing wini the"n'ozzlei shown in. Figure pi efe'r'a'bleto pump the cellulose acetate solution through the 'innertubular member 81 and the'circular'orifice 83}; and th e precipitant through the annular passageway 86-- and the'annular orifice 88,. but thesepositions maybe reversed.

The. invention is further illustrated by the following example, in which the device shown in Figures 1 and 2 of thedrawing'is employed; the parts given are by weight.

' Example A soIutionof-an hcetone-soluble cellulose acetate in.

about 3 times its Weight of a aqueous acetic acid at; 65'i70 C. was obtained by pretr'eating cellulose with. acetic acid, acetylating the pretreated cellulose using rnethylene chloride' as the solvent and sulphuric acid as catalyst, ripening the cellulose acetate after: adding water,-

acetic acid-and further sulphuric acid, distilling olf the ,methylene chloride, and neutralising the sulphuric acid.

C; bypassing hotwater through the jacket 13, and was filled with aqueous acetic acid of concentration about. 14% and at about 70 C. up to'the level of the overflow discharge duct 12. The ripened solution, still at a temperature of 65 70' C., was forced downwardly through the middle annular orifice 46 of the nozzle shown in Figure 2, while aqueous-acetic acid of concentration between 7.4 and 14% and at a temperature of 70 C. was forced through the inner annular orifice 53 and the outer annular orifice 45. Simultaneously further. aqueous acetic acid of concentration about 14% and atabout 70 C. was fed into the vessel 10 through the inlet 11. The streams of cellulose acetate solution and aqueous acetic acid extruded from the nozzle impinged on the surface of the liquid inthe vesel and were rapidly and thoroughly intermixed, precipitating the cellulose acetate. The precipitate quickly become dispersed throughout the body of aqueous acetic acid in the vessel, by means of which it was carried out of the vessel through the overflow discharge duct 12. The precipitate was then separated from the acid liquid by decantation. It had the form of a very fibrous flake of low bulk density, and was readily Washed substantially free from acid.

While the invention has been described with particular reference to the production of cellulose acetate and its precipitation from solution, it is of value also in the production and precipitation of other organic substances of very 'high molecular weight, especially cellulose esters such as cellulose propionate, butyrate, acetate propionate, acetate butyrate, and acetate stearate, and cellulose ethers, for example water-soluble methyl cellulose and water-soluble and organic solvent-soluble ethyl celluloses. Examples of other compounds of very high molecular weight in the production of which the process of the invention may be used are polyvinyl compounds such as polyvinyl chloride, polyvinyl alcohol, and polyvinyl acetate, and copolymers derived from two or more vinyl or vinylidene compounds, e.g. copolymers of vinylidene chloride and acrylonitrile. Such compounds may be precipitated either from true solutions or from latices, which for the purposes of this specification are included within the term solutions.

Having described my invention what I desire to secure by Letters Patent is:

1. Process for the precipitation of a cellulose ester of at least one lower fatty acid having 2 to 4 carbon atoms in the molecule from solution in a solvent which is a liquid at ordinary temperatures, which comprises causing an unsupported stream of the solution, and at least one unsupported stream of a precipitant flowing parallel to and in contact with the stream of solution in such a way that the stream of solution'is substantially completely surrounded by precipitant, to impinge on the suraaawe of the unsupported streams of solution and precipitant,

occurs before they reach the surface of the body of precipitant.

4. Process according to claim 1, wherein the amount of precipitant in the unsupported streams is at least such as would be sufficient to precipitate substantially the whole of the cellulose ester in the said streams on intimate mixing of the streams in the absence of additional amounts of precipitant.

Process for the precipitation of cellulose acetate from solution in acetic acid by means of a precipitant selected from the group which consists of water and aqueous acetic acid of concentration below 40%, which comprises causing an unsupported stream of the solution and at least one unsupported stream of the precipitant, flowing parallel to and in contact with the stream of solution in such a way that the stream of solution is substantially completely surrounded by the precipitant, to impinge onthe surface ot ,a body. of precipitant which. is deep enoughv to absorb substantially. the whole of the momentum of,

the said streams wher'eby the said streams of solution and precipitant .are rapidly and intimately mixed.

6. Process according to claim .5, wherein the solution travels at a lower-"linear speed than the precipitant.

7. Process according toclaim 5, wherein an annular stream of the solution -fiows between an inner stream and an outer annular stream of the precipitant.

8. Process according to'claim 5, wherein a fiat stream of the solution flows between two flat streams of the precipitant. I I

References Cited in the file of this patent p UNITED STATES PATENTS 1,567,482 Anthony e Dec. 10, 1919 1,859,992 Seil May 24, 1932- 1,948,625 Mason Feb. 27, 1 934 1,949,213 Mason Feb. 27, 1934 2,527,689 Suthardet a1. Dec. 11, 1946 2,534,253 Fash Dec. 19, 1950 2,622,273- Detwiler Dec. 23, 1952. 2,647,103 Grifiith etal. July 28, 1953- Paladino Mar. 1, 1955- 

1. PROCESS FOR THE PRECIPITANT OF A CELLULOSE ESTER OF AT LEAST ONE LOWER FATTY ACID HAVING 2 TO 4 CARBON ATOMS IN THE MOLECULE FROM SOLUTION IN A SOLVENT WHICH IS A LIQUID AT ORDINARY TEMPERATURES, WHICH COMPRISES CAUSING AN UNSUPPORTED STREAM OF THE SOLUTION, AND AT LEAST ONE UNSUPPORTED STREAM OF A PRECIPITANT FLOWING PARALLEL TO AND IN CONTACT WITH THE STREAM OF SOLUTION IN SUCH A WAY THAT THE STREAM OF SOLUTION IS SUBSTANTIALLY COMPLETELY SURROUNDED BY PRECIPITANT, TO IMPINGE ON THE SURFACE OF A BODY OF PERCIPITANT WHICH IS DEEP ENOUGH TO ABSORB SUBSTANTIALLY THE WHOLE OF THE MOMENTUM OF THE SAID STREAMS, WHEREBY THE SAID STREAMS OF SOLUTION AND PERCIPITANT ARE RAPIDLY AND INTIMATELY MIXED. 